Lubricant



Patented Mar. '11, 1947 72,417,283 H LUBRICANT i John C. Zimmer and George M. McNulty, Union,

N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application December 23, 1942,

Serial No..469,914 8Claims. (o1. 25.2-48.6)

The presentinvention relates to an improved extreme pressure lubricant and sulfurized cutting oil base and the method of preparing the same. More specifically the present invention' is concerned; with thelsimultaneous sulfurizing of particular oil blends to yield a sulfurized mineral oilsoluble base which can then befi'ncorporated in v mineral lubricating oil for use as an extreme pressure lubricant or cutting oil. As a cutting oil, the mineral lubricating oil and "sulfurized blend can be used without modification or emulsified with water.-

Experience has shown that many oils will, on heating, react with or absorb. elemental sulfur,

and that theaddition of sulfur tooilwill improvethe lubricating qualities of the oil, particularly when subjected to heavy loading. -Generally speaking, the load-carrying characteristics of an oil improve in proportion to the increased amount of reactive sulfur content. About of the sulthe tan 01 1 contains as little as 30%01' sulfur.

Fatty oils, such as lard oil, sperm oil, etc. have been succes fully. used as sulfurized cutting oil bases; however oils of .thistype are getting progressively scarcel and are: more costly, and anacceptable? substitute therefor is very much needed.

The principal object of the present invention is the production of asulfurized product, solublein mineraloil and which'ca'n be blended with mineral lubricating oil to'give a product suitable for use as either an extreme pressure lubricant or a sulfurized cutting oil bas.' This and. other objects will be apparent to those-skilled in the art upon reading the followingldescription.

It has now been discovered that an admixture of tall oil, either crude. or refined andan.

ester of a high molecular weight fatty facid and furized oil is blended in about 90% '01" mineral lubricating oil to form a cutting oil. A good cutting oil should carry 15' weights gradual loading and a minimum of-7v weights shockloading on the Almen machine. Full details of-the Almen machine test are to be found in Proceedings American Petroleum Institute, 13th annual meeting, Nov. 14-17, 1932. Considerable objection-to the sulfurized cutting oils of the prior art has been raised clue to the fact that they exhibit a decided tendency 'to deposit sulfur or sulfur reaction products.

One type of oil which has found considerable application as a sulfurized cutting oil base is tall oil, which is a mixture of fatty and rosin acids occurring in pine and: other non-deciduous woods, and is obtained as a by-product in paper manufacture. For conversion to a cuttingoil base the tall oil may be used either in its crude form or purified by distillation. Tall oil, either'crude or refined, will absorb about 40% of sulfur. At about 20% sulfur content the product is absolutely non-reactive to copper, however, the Almen loads are very low for a product containing this amount of sulfur, due to "complete reaction between the I sulfur and tall Oil. The addition ofeabollt 40% of sulfur to tall oil is required to give satisfactory Almen loads, but such a'product is quite insoluble in' mineral oil. Oil-solubility is determined by blending about 10% of the sulfurized product in of a Mid-Continent viscoscity S. S. U. at 100 F. mineral oil, letting the .blend stand for 7 days at either 0 F., 45 F. or room temperature, and determining the amount of sediment. Some tests include all three temperatures. A completely soluble sulfurized basewill form no sediment. A 9:1 blend of mineral: oil.and tall oil containing 40% of sulfur will, on standing, show a sediment of from 5 to 10% which denotes that 50% or more of the sulfurized tall oil is mineral oil insoluble. The mineral oil insolubility of sulfurized tall oil is quite perceptible when a monohydric alcohol ofIat leastflflcarbonlatoms, when sulfurized will give .a product which readlly' pours atroom temperature and-which .willv readily dissolve in mineral lubricating.oil.';. In; general the methodconsists in admixing tall' oil, f Q ester and sulfur monochlor'idefSzCli a'n'dhea'ting until allof thesulfur has goneinto solution, which reaction will require from about 1-5.hours.'

The present invention contemplates the 'u'se of I h I amixture ofoils,one1being tall oil, andthefloth being anester of a fatty acid and a monohydr" alcohol in which the mixture is composed of :fr"

40-60% of tall .011 and from so -40% of the. ester. As previously-stated the esters are goleagenousy,

materials, resulting from the combination v,of a monohydric alcohol and a high molecularweight 5 fatty acid andfmay be obtained either asanatural product or produced synthetically. Itis pre-. ferred to use such esters either naturally occurring or synthetic as contain an excess of alcohol. Specific examples of such. esters are sperm oil, lauryloleate and cetyl oleate although many other esters ofa similar nature may be employed. Sperm oil isa naturally occurring oil. obtained from the sperm whale and is composed chiefly of cetyl palmitate.

Sulfur is incorporated into the oil mixture by f v reacting the oils with either l'sulfur'yor rsulfur monochloride. The reaction is conductedso as to incorporate from 15-25% of sulfur inthe'oil. When using sulfur preferably as flowers of sulfur, the sulfurizing reaction occurs at from 350-400-F. and preferably from 370-390 F.' If

sulfur monochloride 'is'utilized as the source of it sulfur the temperature of the reaction must be materially reduced and carefully controlled to prevent undue polymerization and the sulfurized product must'be purified as by water washing I p For'reaction' with sulfur monochloride the temperature should the limits of 1o0. 20o F;,;preferto remove chlorine by-products.

be held within ably -180 F.

Although a wide range of lubricating oils may be improved intheir lubricatingand load'bearing cha'matasacsby the addition'theretooi the sulfurized'oils of'the present invention, in general the lubricating oils'comprise oils having a furiz'ed iicuttirig oiljbas the. copper test, 'a strip-of polished'copper viscosityat 100 F.in the range of from about;

wassuspended in abath of the cutting oil blend 90-900seconds, an A. P; I. gravity of 2 3 ,-33, and 5 maintained at a temperature of F. for-a a-flash point above 300 F. However. it is pre period .of f3 ho'urs. 'l he results of these tests are ferred touse paraflinicand'naphthenicbase oils given in the followingtable.

i Table V r 1 r Almen weights 8 1 EH 0 11 l l sulfurized cutting oil base per cent Copper test 1;; U j Gradual Shock. spdimpnmn'nn 7 U V I loading loading sulfurized ta'l] oil l')% S I 8' L None Pass; l v 'Sullurized tall oil (%8 0. I 13 2 i Do.' H '.-.SulIuri zed tall or! (30% S 15 a 5, 4 ,6 Slight stain. Sullunzedtail oil (40% S) l5 ll J 8-10 Blackened. r "40%lsllo1l;-40%spcrmo1l V D 15 .11 None Pass. a

37.5% talloll,37.5% sperm oil, su l5 11 None -Do. tall oil, 45% sperm oil, 25%suliur l5 4 9 2L7 Do. 40% tall oil,- sperm oil, 15% sullur- 15: 9 0.8 Do.

i sulfurized bases were compounded inthe manner described in the example above I This sulfurized base was compounded by mixing equal parts ol telloil containin a pi on bohtaining 10% 5 lhis sulfuiizedjaasewas compounded by mixing eoual parts of talLoil containing 2l;% S and sperm oil cone ieB- having agravity time range of from 23A. R1. to 28? A ;.-P. I., and-a viscosity 'at"100 90 to-' OW'second'si- I r I In king up the E. P Qlubrica'nt and-sulfurized cutt g ilfbaseofftheipresentinvention the oils are, I placed in; acdoking vessel and heated to the r ac ion temperature which for elemental sulfur is'fro'ni '300-460;F.' and for sulfur monochloride from 100 200 F. depending largely upon the time i a'vailable for completingthe reaction,

F. of from andffth'ef'sulfur or sulfur "halide is then" added.

The temperature is maintained and the reactants stirred for a'p eri'od of from 1-5 hours to insure satisfactory sulfur retention." After the "reactio' "is"completeidetermined b'y'i-rapi'dly cooling a smallportion and determining 'if sulfur 'se'p lzed' product is perature.

' aratesj. heating is discontinued 'andthe sulfur- 5 permitted to cool to room tem Where sulfur "monochloride is used be air -blownior 30 minutes to remove chlorine and chlorinated products; The product at room temperature is liquid; flows orv pours readily and is soluble in parafiinic mineral lubricating oils in all proportions. It isthen :ready for blending with a mineral lubricating oil to yieldan E.- P. lubricant or cutting oil. Peri-blending purposes it is preferred touse from '5-20%. of the sul-n furized. cutting oil base, the percentage being calculated on the basis ofathetotal composition.-

The following specific example is given for the purposeofillustrating the invention, thus leading toabetter uhderstanding thereof.

anlext ernally heated kettleequippedwith af'stirre '60 EXAMPLE v r Percent Tall: oil acids 37.5 Sperm 7 37.5 Sulfur 25.5),

and'heated to a temperatureof 370F. The. sulfu was" then stirred in and the temperatureheld between 370? FQ'and 390 F. for one hour. Heating wasth en discontinued and the-sulfurized oil was permitted to cool to room temperature;

Several cutting oil blends were made up using9 parts by weight of .a mineral lubricating oil, 110

vis. at 100"F. for each part by weight of sul- What is claimed isa andr-a-high molecular weight fatty acid: 2.- As a composition of matter; a mineral weightfatty acid is lauryl oleate.

4. A composition as definedin cla the ester is cety-l'oleate. I j

5. As a :compositionof. matter: a 5mineral=oil-.. Vi soluble .-cosulfurized cutting .011 base comprising. from 53-25%. of sulfur vand from 95.45% of 'ablend of tall oil and-an ester of a monohydrlc I alcohol of at least "10 carbonatoms With-a high molecular weight fatty acid, in which blend the percentage of tall oilranges from 60-40%. V

6. The method of. producingia sulfurized cut-f ting oil base whichcomprises belnding tall oil a with an ester of a monohydric alcohol of at least, 10 carbon atoms with -a -.high-moleculartwelghtg 1' fatty-acid,heatingthe blend to, a sulfurizing 7 temperature and reacting the blend with; sulfur.

7 ..The method of producing, a sulfurized'cut weight fatty, acid.

' RE R N ES CITED file-of this patent: v

' 'UNITEDMSTATESPA'IENTS 1 V r The followingLreferences are of record in the Number Name f Date 7 2,012,446 Edwards Au 27,1935

2,179,066 Smith' Nov.57, 1939. 2,198,562 Pollak Apr. 23, .1940.

. testeda for jiloadcarrying ability, solubility and copper. corrosion.

011-. soluble sulfurized'cutting oil base. comprising a cosulfurized blend of tall oil and sperm oil; 1 3. The composition as defined in' 'claim liinf which the ester of.a-monohydrictalcohol of ,at least 10 carbon. atoms with a high molecular 1m 1' ashes; E

C. Z IMMER QE R E' Puryear Mar.-12, 1940 

